Opaque white coating composition comprising essentially cellulose ester/cross-linking agent/catalyst/solvent and organic liquid

ABSTRACT

A coating composition and method of obtaining same by mixing an organic solvent which contains at least 85% by volume paraffinic hydrocarbons and has a boiling point of at least about 300*F with a cross-linkable resin lacquer. An opaque coating can be obtained by applying the composition to a substrate and heat curing same thereon.

Unite 11 States Patent Eiland OPAQUE WHITE COATING COMPOSITION COMPRISING ESSENTIALLY CELLULOSE ESTER/CROSS-LIN KING AGENT/CATALYST/SOLVENT AND ORGANIC LIQUID Appl. No.: 526,640

Related US. Application Data Division of Ser. No. 410,684, Oct. 29, 1973, Pat. No. 3,869,305, which is a continuation-in-part of Ser. No 170,647, Jan. 29, 1974, Pat. No. 3,788,886, which is a continuation of Ser. No. 781,977, Dec. 6, 1968, abandoned.

US. Cl 260/14; 260/2.5 R; 260/13;

260/15; 260/17 R; 427/373 Int. Cl. C08L 1/10; C08L 1/14 Field of Search 260/15, 14, 2.5, 17 R,

260/22 CO, 22 EP, 33.6 R, 33.6 EP, 33.6 VA, 850; 427/373 *Dec. 23, 1975 [56] References Cited UNITED STATES PAT ENTS 2,469,348 5/1949 Young et a1. 260/15 2,875,164 2/1959 Ballet a1 260/15 3,020,172 2/1962 Mohnhaupt.... 117/36.7 3,031,328 4/1962 Larsen l17/36.7 3,118,853 1/1964 Hart et al 260/834 3,265,645 8/1966 Coney et a1 260/ 15 3,370,025 2/1968 Salo et al. 260/15 3,655,591 4/1972 Seiner 117/36.7 X

y FOREIGN PATENTS OR APPLICATIONS 715,517 8/1965 Canada 117/36.7 1,518,715 3/1968 France 117/367 Primary Examiner-Donald E. Czaja Assistant ExaminerEdward Woodberry Attorney, Agent, or Firm-John P. Taylor, Esq.

[57] ABSTRACT A coating composition and method of obtaining same by mixing an organic solvent which contains at least 85% by volume paraffinic hydrocarbons and has a boiling point of at least about 300F with a crosslinkable resin lacquer. An opaque coating can be obtained by applying the composition to a substrate and heat curing same thereon.

7 Claims, N0 Drawings OPAQUE WHITE COATING COMPOSITION COMPRISING ESSENTIALLY CELLULOSE ESTER/CROSS-LINKING AGENT/CATALYST/SOLVENT AND ORGANIC LIQUID CROSS REFERENCE TO RELATED APPLICATIONS This application is a division of U.S. Pat. application Ser. No. 410,684, now U.S. Pat. No. 3,869,305, issued Mar. 4, 1975 filed Oct. 29, 1973, as a continuation-inpart of U.S. application Ser. No. 170,647, issued Jan. 29, 1974 as U.S. Pat. No. 3,788,886, and filed Aug. 10, 1971 as a streamlined continuation of U.S. Pat. application Ser. No. 781,977, filed Dec. 6. 1968, now abandoned.

This application is, therefore, also related to US. Pat. application Ser. No. 170,369, now U.S. Pat. No. 3,823,101, issued July 9, 1974, and filed Aug. 9, 1971 as a division of U.S. Pat. application Ser. No. 781,977.

BACKGROUND OF THE INVENTION This invention relates to a coating composition. More particularly, it relates to preparation of a lacquer which when applied to a substrate such as wood, metal or the like produces an opaque coating thereon.

Resin lacquer coatings prepared by use of a portion of the solvent which is compatible with but not completely soluble in the remainder are known. Coney et al U.S. Pat. Nos. 2,875,164, 3,265,645 and 3,282,716 teach employment of a multi-component solvent and involve cellulose ester/urea formaldehyde lacquers which, when applied to a substrate may be cured thereon by cross-linking to a clear, high-gloss film. It is also known to add pigments to such lacquers to obtain white rather than clear coatings. Such pigments, however, are relatively expensive, and to obtain the desired degree of whiteness usually 8-10 pounds of lacquer are required to coat a ream of 3,000 square feet. In addition the recycling of used coated containers for purposes of economics and ecology is simplified if the amount of inorganic pigments is reduced. Therefore, development of a coating which permits use of lesser amounts thereof than do prior art coatings and which does not require use of pigments to produce opacity, particularly an opacity or whiteness of the degree desired for use on a substrate such as the aluminum foil conventionally used in packaging mints, chewing gum and the like, represents a highly desirable result. By aluminum 1 mean aluminum and alloys thereof containing at least 50% by weight aluminum.

It is accordingly an object of this invention to provide a coating composition which is basically nonpigmented but which is opaque or becomes opaque when applied to an aluminum or like substrate and cured at an elevated temperature. Another object of this invention is to provide a method for producing an opaque coating which does not require use of pigments. A further object of this invention is to provide a substrate coated with an opaque lacquer. Further objects will be apparent from the description and claims which follow.

SUMMARY OF THE INVENTION In its broader aspects my invention involves mixing a cross-linking catalyst and an organic liquid comprising at least 85% by volume paraffinic hydrocarbons, such as mineral spirits or the like, said liquid having a boiling 2 point of at least about 300F, with a lacquer in which is dissolved a cross-linkable resin and a cross-linking agent.

I will refer to the added organic liquid mixed with the lacquer as the non-solvent, diluent or dispersing phase since it is not a solvent for the lacquer solvent or the cross-linkable resin and cross-linking agent contained therein. As mentioned hereinabove, it must have a boiling point of at least about 300F. Preferably its boiling point is above 325F, and most desirably above 350F. It may contain up to 5% olefins and up to 14% aromatics.

This organic liquid higher-boiling non-solvent, or diluent, is a material which the lacquer (active) solvent and lacquer solids will tolerate without any substantial precipitation thereof. Also, this organic liquid, non-solvent or diluent used as the dispersing phase according to my invention, by taking longer to evaporate due to its higher boiling point, gives time for the desired opacity to develop. Organic liquids useful according to my invention as this non-solvent ingredient are, for example, odorless naphtha or Stoddard solvents, mineral spirits, and mineral oils which have the required boiling point and paraffinic hydrocarbon content. Illustrative higher-boiling liquids useful according to my invention are Sohio 3,440, Sohio 3,454, Shell Oil Company mineral spirits, Sohio Stoddard Solvent 3,039 and Sohio Solvent 140. Atlantic Refining Company Atreol 21 mineral oil was also found to be useful in developing the desired opaque coating. Preferred amount of this non-solvent is from about 12% to about 40% by weight.

The cross-linkable resin may be a cellulose ester, such as cellulose acetate propionate and cellulose acetate butyrate or'an alkyd resin, such as those obtained by condensing and polymerizing phthalic anhydride or other dicarboxylic acid with a polyhydroxy alcohol such as glycerol, modified by fatty acids, drying oils such as linseed, or the like, if desired. Representative cellulose esters useful according to my invention include the propionic and butyric acid esters of cellulose. Particularly useful are those which are soluble in alcohols, e.g., ethyl alcohol, which is a convenient lacquer (active) solvent according to my invention. A representative cellulose acetate butyrate which I have found suitable according to my invention has a butyral range of about 35 to 50%, and a viscosity range of from about 0.1 to 40 seconds. Typical cellulose esters useful in my invention include those ordinarily referred to as halfsecond cellulose acetate butyrates and half-second cellulose acetate propionates and those commonly called alcohol-soluble butyrates and propionates. A typical useful cellulose acetate propionate might have a propionyl content of from about 40 to 55% and a viscosity of from about 0.1 to 50 seconds. Preferred acetyl content for the cellulose esters useful according to my invention is l-l0%. Preferred hydroxyl content of the cross-linkable resin is at least 4% and ranges from about 4 to about 7%.

The crosslinking agent is a compound with which the resin will cross link to form a cured coating. It must be compatible with the cross-linkable resin. Preferred is a condensation polymer. The condensation polymer may be one formed by condensation of a urea-type compound such as urea, thiourea, cyanamide, guanidine, melamine or the like with a lower aliphatic aldehyde (usually an aldehyde containing from 1 to 4 carbon atoms, and most commonly formaldehyde), or with such an aldehyde and an alcohol, for example,

butanol. For example, the urea formaldehyde polymers of the abovementioned Coney et al patents may be used as the condensation polymer.

For example, the specific urea formaldehyde polymer may be dimethylol urea. The urea formaldehyde polymer may be alkylated, for example, such as the butylated urea formaldehyde of above-mentioned Coney et al U.S. Pat. No. 3,265,645. Representative urea formaldehyde resins include American Cyanamid Beetle 216-8 supplied at 60% solids in butanol/xylol, Beetle XB-1047 supplied at 55% solids in isobutanol/xylene and Reichold Chemicals Beckamine P-l96- 60, an alcohol-soluble urea resin furnished at 60% solids. Representative melamine polymers which I have found useful according to my invention include American Cyanamid Cymel 300 and Cymel 301, hexamethoxymethyl melamine resins. Such condensation polymers may be incorporated in the lacquer in unpolymerized, polymerized or partially polymerized form. For convenience 1 will refer to such a condensation polymer as a urea-formaldehyde or melamine polymer.

When applied to a substrate, for example, wood or aluminum, my lacquer may be cured by air drying but preferably is cured by heating to an elevated temperature to accomplish curing by cross-linking of the resin with the cross-linking agent and resultant production of an opaque coating. The cross-linking agent reacts with reactive groups of the cross-linkable resin, for example, the hydroxy groups of cellulose acetate butyrate or cellulose acetate propionate when the cross-linkable resin used is a cellulose ester. It is believed that curing takes place by evaporation first of the lacquer (active) solvent, that is, the solvent in which the cross-linkable resin and the cross-linking agent are dissolved, which may be called the dispersion phase. At this point the coating appears practically clear and in an initial state of cure wherein some rigidity is possessed but not the hardness of a fully cured lacquer. Then the coating cures completely to an opaque color upon evaporation of the non-solvent, or diluent, which has a higher boiling point, that is, the above-defined paraffinic hydrocarbon having a boiling point of at least about 300F. It appears that the non-solvent is dispersed in the lacquer film as minute particles 02- l .5 microns in size (diameter) and when the higher-boiling non-solvent is driven off from the partially cured lacquer film, this leaves spherical voids of the same 0.2-1.5 micron size with resultant light scattering at the airlacquer solids interfaces producing the opacity.

While the foregoing serves as an explanation for the apparent mechanism by which the opaque coating is formed, the formation of the opaque coating is accomplished very rapidly in accordance with the invention by the presence of the acid catalyst and the hydroxyl content specified which apparently enables the crosslinkable resin and the cross-lining agent to react quickly at an elevated temperature to form a crosslinked structure containing the spherical voids. Thus the coating composition can be used in a continuous process for coating coils wherein the coil is coated, cured at an elevated temperature and then rewound immediately.

Preferred concentration of cross-linkable resin and of cross-linking agent is from about 3.3 to about by weight of the resin lacquer without higher-boiling non-solvent and from about 2 to about 20% by weight of the coating composition with higher-boiling non-solvent.

The solvent for the resin/cross-linking agent lacquer or dispersion phase of my invention 1 designate as an alcohol-type solvent as ethyl alcohol is a representative solvent, although this solvent may contain one or more additional similar substances, such as ketones and organic esters, which it is believed help to lessen the gradual increase in viscosity which generally takes place after the composition is made up. The lacquer solvent may contain a high percentage of a lower aliphatic alcohol, for example, the aforementioned ethyl alcohol. Representative components of the lacquer solvent, which may also be called the active solvent, that is, the lower-boiling solvent of the dispersion phase, are methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl cellosolve, ethyl alcohol, isopropanol, ethyl acetate, npropyl alcohol, n-butyl alcohol and the like. Mixtures of two or more of the foregoing may be used. For example, any of the solvents or mixtures of solvents for the cross-linkable resin/cross-linking agent may be the predominantly non-aqueous solvents'used in above-mentioned Coney et al U.S. Pat. Nos. 2,875,164, 3,282,716, and 3,265,645. The active or lacquer solvent (lower-boiling solvent) preferably has a boiling point of less than about 275F. Preferred concentration of this lower-boiling or active solvent for the cross-linkable resin and cross-linking agent is from about 6 to about 60% of the coating-composition of my invention including the higher-boiling non-solvent.

The preferred weight ratio for the amount of higherboiling organic liquid or diluent to solids content of the lacquer containing the cross-linkable resin and the cross-linking agent is from about 0.75:1 to about 1.75:1.

A cross-linking catalyst is essential for fonning the desired amount of white color or opacity developed upon heat curing, that is, in cross-linking the resin with the cross-linking agent. Usually an acid catalyst is used. Representative acid catalysts which may be used according to my invention include the preferred catalysts p-toluene sulfonic acid and methane sulfonic acid and sulfuric acid, plus other alkane sulfonic acids, hydrochloric acid, nitric acid, and the like. Other acid catalysts which may be useful include those of Coney et al U.S. Pat. No. 3,282,716 referred to above, specifically, methyl, ethyl or propyl sulfonic acids, or a mixed alkane sulfonic acid such as described in U.S. Pat. No. 2,875,164. Preferred amount of catalyst useful according to my invention is from about 0.035 to about 1.7% by weight of the lacquer without the higherboiling solvent (this percent not including the butyl alcohol or other diluting solvent for the catalyst to give, for example, a 25% solution of catalyst such as sometimes useful) and from about 0.025 to about 2% by weight of the lacquer with higher-boiling point solvent added thereto. Aging the catalyst, for example, by boiling for two hours and then storing at room temperature for a week or two, tends to result in a somewhat more stable coating composition and to prevent premature curing or failure to form the desired amount of white color or opacity.

Conventional plasticizers which may be used in the coating composition of this invention, preferably in amounts up to about 4% by weight of the total composition containing the higher-boiling liquid or diluent, include the preferred triphenyl phosphate and 2-ethyl hexyl diphenyl phosphate, plus chlorinated biphenyl, chlorinated triphenyls, dioctyl phthalate, and the like. Blends of plasticizers may be used, for example, a blend of dioctyl phthalate with a more active plasticizer.

According to my invention there may be used up to about of one or more modifying resins based upon the weight of the coating composition including the diluent. For example, one or more of the following may be used to modify viscosity and improve final toughness, adhesion, and water resistance of the lacquer when coated and cured on a substrate: epoxy resins such as Shell Epon 836, Epon 828 and Epon 1,004, which are epichlorhydrin-bisphenol A type polymers ranging from liquid to solid resins and ranging in epoxide values from about 180 to about 1025; phenolic resins such as General Electric Methylon 75108, blocked isocyanates such as disclosed in US. Pat. No. 3,650,788, and polyvinyl butyral resins such as Union Carbide XYHL, and the like.

If it is desired to add color to the opaque coating formed by curing of the coating composition according to my invention or to produce an even higher degree of whiteness, dyes and pigments may be added in amounts up to about 12% by weight. Slip agents such as talc, mineral oil, dimethyl silicone polymers, and graphite may also be added in similar amounts to reduce the coefficient of friction of the surface of the particular substrate coated with the cured coating composition according to my invention.

Small amounts of other conventional additives such as antioxidants may also be used in the coating composition of my invention provided they are compatible with the other ingredients and not reactive in such a way as to destroy the desired opaque color when it is coated on a substrate.

According to my invention the dispersing phase, that is, the higher-boiling organic liquid, diluent or non-solvent, should be added to the mixture last, preferably just after the addition of the catalyst. It should be mixed with the remaining ingredients sufficiently to cause the desired droplets to form. If a clear dispersion does not result at first, continued mixing will produce one. That is, there should be enough mixing by stirring, shaking, or the like to disperse any gel which may be formed and to form an almost clear solution.

It is preferred in preparing the coating composition, prior to spreading it on the substrate and curing it by cross-linking, that the cross-linking agent be added to the lacquer just before addition of the catalyst and the higher-boiling solvent, which, as just explained, are added last. This will help to prevent premature curing.

It should be noted that the coating composition of the invention contains a cross-linking catalyst and a specified hydroxyl content in the cross-linkable resin to enable one to heat cure the coating without loss of opacity as in prior art coatings. However, the coating can be aircured.

If the required cross-linking of the resin with the cross-linking agent is obtained by air curing, usually about 24 to 96 hours are required after application to substrate to obtain a satisfactory degree of whiteness or opacity. When curing is accomplished by heating, a temperature of about 250 to 750F is preferred. Best development of opacity is at 650750F for from l60 seconds.

The coating may be applied by spraying, rolling, brushing or the like. One way is to use a gravure roll and a web containing the coated substrate run at 200-300 ft/min directly into an oven at 400750F. In such a procedure the several steps involved in producing the desired opaque coating are accomplished in rapid succession. First the active solvent is driven off. then the non-solvent or diluent droplets become distributed in the lacquer, with the resin cross-linking with the cross-linking agent and becoming semi-rigid to rigid, and finally the higher-boiling non-solvent being driven from its entrapped globular form to leave minute voids which develop the desired opacity.

The amount of lacquer applied, when used on foil, is usually about 0.5 to 5 lbs/3,000 sq. ft., preferably l-3 lbs/3,000 sq. ft., that is, a sufficient amount to result in a coating thickness of about one-tenth to /2 mil or 0.000] to 0.0005 inch.

The following examples are illustrative of the invention.

EXAMPLE 1 A formulation containing 31% non-volatile material was made as follows:

The butyrate used was ethyl alcohol-soluble, and the sole lacquer solvent in this example was ethyl alcohol. Curing was effected by reaction of urea formaldehyde with hydroxy groups of the butyrate.

Thirty-one grams of odorless mineral spirits were added to grams of the above lacquer in a bottle. The bottle was then shaken for about 30 minutes on a paint shaker to disperse the mineral spirits in the lacquer. The lacquer was then applied at about 2 pounds of dry lacquer solids per 3,000 sq. ft. on 1,145-0 aluminum foil of about 0.002 inch in thickness. On drying with a small hand dryer to remove alcohol, an almost transparent coating with very little tackiness was first formed. The coated foil was then placed in a forceddraft oven at 400F for 15 seconds to drive off the mineral spirits and complete the cross-linking cure. A highly opaque white coating was produced.

Thin layers of this coating when viewed at 700X magnification with transmitted light showed very small, tightly packed spheres or bubbles. In an electron microscope at 20,000X and 50,000X the bubbles appeared to be almost perfect spheres. The spheres appeared to be in the approximate range of 0.2 to 1.5 microns in diameter. Electron micrographs were made.

The white coating had good adhesion to annealed foil and fair adhesion even after water immersion. It also showed good scuff resistance and did not lose whiteness on applying an over-print lacquer. It did not blacken or lose whiteness when placed in a heat sealer at 280F and 30 psi for 1 second.

EXAMPLE 2 The following formulation was made and coated on annealed foil, the foil used being toluene-cleaned and consisting of 3003-Hl9 aluminum alloy:

-continued Pounds Material resin 1.50 Phenolic resin 30.30 Solvent [in parts, 25 MEK (methyl ethyl ketone), 46.2 isopropanol, 28.8 ethyl acetate] 22.0 Odorless mineral spirits Part B 11.36 lb 60% urea formaldehyde resin and 0.20 lb paratoluene sulfonic acid were added to Part A.

This composition was applied to annealed foil, toluene-cleaned 3003-H19 foil, 0.009 inch 3105 toluenecleaned aluminum sheet, primed 0.009 inch 3105 aluminum sheet and aluminum sheet and primed foil. 1t adhered well in all cases and withstood pasteurization in hot water. It also gave good adhesion to metal decorating inks, and overprint lacquer satisfactorily took an overbake and withstood forming.

EXAMPLE 3 The following formulation was made up and applied to aluminum foil. The butyrate and epoxy resin solutions were mixed separately and allowed to cool to room temperature before use. The B part was added and mixed with the lacquer just before use, the mineral spirits being added last. Addition of the mineral spirits caused gel formation which was dispersed to form an almost clear solution upon further mixing. The resulting lacquer contained 20.7% solids. Viscosity of the freshly made solution was 23 seconds, No. 2 Zahn cup. The viscosity increased to about 40 seconds over three days. The lacquer was applied on an lnta Rota machine with a 65 line helix roll and a smoother bar to give 2.5 lbs/3,000 sq. ft. on 0.0035 inch 1 145-0 aluminum foil. The temperature was raised to about 400F to develop the desired whiteness. The same composition was also applied at the rate of 1.4 lbs/3,000 sq. ft. Application was similar except that no smoother bar was used.

A Solution The B materials were added to the A solution just before using on the coating machine.

Urea-formaldehyde Solvent (25.2% MEK 28.87: ethyl acetate 46.07: isopropyl alcohol by wt) p-Toluene sullonic acid solution (25% in n-hutyl alcohol) (This solution was boiled two hours before use.)

()dorless mineral spirits EXAMPLE 4 A coating composition substantially the same as that of Example 3 was prepared except that only 0.8 gram of catalyst and 22.0 grams of mineral spirits (Sohio 3,440) were used. Upon evaporation at the higher-boiling temperature required to evaporate the mineral spirits, the small spheres of mineral spirits which were trapped within the lacquer composition were driven off to leave small'spherical voids. A white opacity resulted. Sohio 3,454 hydrocarbon liquid was then used in place of Sohio 3,440 as the higher-boiling non-solvent. Both of these liquids have an initial boiling point above 350F, and both are straight aliphatic materials with no aromatics. The KE value for both is around 26 or 27. Other higher-boiling non-solvents were also tried, including Shell Oil mineral spirits with a boiling range of 324 to 398F and an aromatic content of 16%, Sohio Stoddard solvent 3,039 and Sohio solvent 140, with boiling ranges similar to the Shell mineral spirits. Atlantic Refining Company Atreol 21 mineral oil was also used with a somewhat lesser degree of whiteness resulting.

EXAMPLE 5 To determine amounts of higher-boiling organic liquid which will give the desired whiteness, various amounts of Sohio 3,440 mineral spirits were added to a composition substantially the same as that of Example 4 except for the amount of mineral spirits. The mineral spirits were used with 65.82 grams of solution. The following table shows the degree of whiteness produced after coating and curing.

Table Appearance Coating whiteness Mineral Spirits (g) 8 Sfinall amount of whiteness A lacquer of the following composition gave good whiteness when applied to aluminum foil and cured thereon.

Weight Percent 10.44 Butyric acid ester of cellulose 1.83 Epoxy resin 2.30 Phenolic resin 2.30 PlasticiZer 10.44 Ureaformaldchyde resin .31 Catalyst 72.38 Solvent (27.6% solids) 3731* Mineral spirits (ratio of mineral spirits to solids 1.35:1 1

*37.3 grams of mineral spirits added to 100 grams of preceding lacquer *37.3 grams of mineral spirits added to 100 grams of preceding lac quer.

The butyrate ester of cellulose, which contained about 1.6 /2 acetyl and about 4.5% hydroxy, was dissolved in solvent. Use of a high speed mixer results in a rise in temperature. The solution was allowed to cool. Then the epoxy resin was added as a 20% by weight solution. Then the phenolic resin and plasticizer were added. Then the ureaformaldehyde resin was added. Just prior to use, the catalyst, 25% p-toluene sulfonic acid in butanol, and mineral sprits were added. When the mineral spirits were added, some gelling occurred. This was caused in the area of liquid where the mineral spirits were poured into the solution. On mixing for a short time with an ordinary propeller type mixer the gel disappeared once the active resin solvent was thoroughly mixed with the mineral spirits, and a clear solution resulted.

The viscosity of the solution at the beginning was 23 seconds on a No. 2 Zahn cup and rose to about 27 seconds in eight hours.

This solution may be applied by means of a coating bar, by roto-gravure or by other methods to aluminum foil or other substrates. Air drying results in a white coating. Somewhat better filmproperties may be obtained when curing is done at higher temperatures. A tough solvent resistant and waterresistant high opacity film is obtained when the coating is applied to 0.002 inch-thick annealed aluminum foil and then dried at 450F for seconds in a force-draft oven.

EXAMPLE 7 10.8 grams of a 10% solution of Geigy Chemical Corp. lrgacet Scarlet GL dye were added to 100 grams of the solution of Example 6 to produce an-opaque scarlet color. The Irgacet dyes are solvent-soluble hydroxyazo metal complexes.

EXAMPLE 8 EXAMPLE 9 10.8 grams of lnterchemical Corp. Molybdate Orange No. 2,613 epoxy pigment dispersion were plasticizer.

EXAMPLE 1 1 The following formulation was applied with a No. 16 wire wound coating bar at 3.4 mg/sq. in. to 0.002 inchthick 1 145-0 annealed foil.

Amount Material (Grams) 8.7 Alcohol soluble cellulose acetate propionate (5.4% hydroxyl content) (Eastman Kodak) 14.5 P-196-60 urea formaldehyde resin (Reichold Chemical) 59.8 solvent mix 12.0 Sohio 3440 odorless mineral spirits 1.2 p-Toluene sulfonic acid solution (25% in N-butanol) The solvent mix, in parts by volume, was as follows:

Parts Material methyl ethyl ketone 50 ethyl acetate 33 isopropanol 10 N-propanol The coated foil was placed in a forced-draft oven at 450F for 15 seconds. Upon removal the coated foil was found to have developed good opacity although the adhesion of the coating to the foil was not as good as the butyrate coatings.

EXAMPLE 12 To improve the adhesion of the propionate coating several formulations were prepared using epoxy and blocked isocyanate resins. The solvent mix used was the same as in Example 1 1 Formulas in grams Material Cellulose acetate propionate (6.671 hydroxyl) Alcohol soluble cellulose acetate Solution A Solution B Solution C propionate (5.47: hydroxyl) (Eastman Kodak) Cellulose acetate propionate resin (4.3% hydroxyl) Blocked isocyanate (Dupont Mondur S) solvent mix 2nitropropane added to 100 grams of the solution of Example 6 to give an opaque orange color. No. 2,613 orange consists of molybdate orange dispersed in an epoxy resin with solvents. The composition is pigment 15% epoxy resin 1001 15% butyl alcohol 15% toluol.

EXAMPLE 10 2.8 grams of lnterchemical Corp. Midas Gold No. 9604 butyrate chips were added to grams of the solution of Example 6. When the coating composition Each of the preceding solutions was respectively added to the following formulations.

1 1.4 P-l9o-o0 Reichold Chemical ureaformaldehyde -continued Amount Material (grams) 12.0 Sohio 3440 odorless mineral spirits 1,2 p-Toluenc sulfonic acid solution (25% in N-hutanol) Each of the formulations was applied and cured as in Example 1 1.' The coated foils containing the 6.6% hy-' droxyl and 5.4% hydroxyl cellulose acetate propionate I resins exhibited very good opacity. The foil coated with the formulation containing the 4.3% hydroxyl cellulose acetate propionate showed fairly good opacity--but not as good as the higher hydroxyl content resins.

Another foil was therefore coated with the 4.3% hydroxyl propionate resin using a 6.8 mg/sq. in. coating thickness instead of the 3.4 mg/sq. in. thickness. Good opacity was obtained for this coating thickness. In all instances good adhesion of the coating to the foil was observed.

EXAMPLE [3 To the formulation prepared from Solution B in Example 12 was added 8.0 grams of Whittier, Clark and Daniels No. 2755 talc, 1.7 grams of Davidson Chemical Co. Syloid 308 silica to give a matte finish to the coating. To aid in the dispersion of the fillers and flow of the coating 0.08 grams of Tamol 731-5 and 0.17 grams of Raybo Chemical Co. Raybo 3 was added.

The coating was applied to 0.001 inch 1145-0 annealed foil by a gravure coater with a 69 line helical roll at about 100 ft/min. The foil was passed, at the same speed, through a first oven zone (of 6 ft. length) at 350F and then through a second oven zone (of 6 ft. length) at 650F. The opacity and adherence of the resultant coating was good.

While the invention has been described in tenns of preferred embodiments, the claims appended hereto are intended to encompass all embodiments which fall within the spirit of the invention.

What is claimed is: i

1. A coating composition capable of forming an t 12 thiourea, (3) cyanamide, (4) guanidine. and (5) melamine reacted with a compound selected from the group consisting of (l) a lower aliphatic aldehyde and (11) a lower aliphatic aldehyde and alcohol; (0) a solvent for said resin and said cross-linking agent; (d) an acid catalyst adapted for cross-linking said resin with said cross-linking agent; and (e) an organic liquid adapted for mixing with the balance of said composition to form globules therein, said organic liquid comprising at least 85% by volume paraffinic hydrocarbons and having a boiling point of at least about 300F.

2. The composition of claim 1 wherein the cross-linkable resin is a cellulose acetate butyrate or cellulose acetate propionate.

3. The composition of claim 1 wherein the organic liquid comprises mineral spirits or Stoddard solvent.

4. The composition of claim 1 wherein said catalyst is selected from the class consisting of p-toluene sulfonic acid, alkane sulfonic acid, sulfuric acid, hydrochloric acid, and nitric acid.

5. A coating composition adapted to form an opaque color when applied to a substrate and cured thereon, said'coating composition consisting essentially of (a) 2 to 20%by weight cellulose acetate butyrate or cellulose acetate propionate having an hydroxyl content of from 4-7%; (b) 2 to 20% by weight of a condensation polymer of a compound selected from the group consisting of 1 a urea compound, 2) thiourea, 3) cyanamide, 4) guanidine, and 5) melamine reacted with a compound selected from the group consisting of l) a lower aliphatic aldehyde, and 2) a lower aliphatic aldehyde and alcohol; ('c) 6 to 60% by weight solvent for said propionate or butyrate and said condensation polymer; (d) 0 to 4% by weight plasticizer; (e) 0.025 to 2% by weight acid catalyst adapted for promoting cross-linking of said butyrate or propionate with said condensation polymer; (f) 12 to 40% by weight hydrocarbon-type organic liquid adapted for mixing with the balance of said composition to form globules therein, said organic liquid comprising at least 85% by volume paraffinic hydrocarbons and having a boiling point of at least about 300F; and (g) 0 to 10% by weight modifying I resin.

6. The composition of claim 4 wherein said catalyst is aged prior to addition to said composition by boiling the catalyst in a higher-boiling point solvent for about 2 hours and storing the boiled catalyst for at least a week prior to use.

7. The composition of claim 5 wherein the modifying resin is an epoxy, phenolic, blocked isocyanate, or 

1. A COATING COMPOSITION CAPABLE OF FORMING AN OPAQUE COLOR WHEN APPLIED TO A SUBSTRATE AND HEAT-CURED THEREON AT A TEMPERATURE AS HIGH AS 750*F, SAID COATING COMPOSITION HAVING AS ESSENTIAL INGREDIENTS (A) A CROSS-LINKABLE CELLULOSE ESTER RESIN HAVING AN HYDROXYL CONTENT OF AT LEAST 4%; (B) A CROSS-LINKABLE AGENT IS A CONDENSATION POLYMER OF A COMPOUND CROSS-LINKABLE AGENT IS A CONDENSATION POLYMER OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF (1) A UREA COMPOUND, (2) THIOUREA, (3) CYANAMIDE, (4) GUANIDINE, AND (5) MELAMINE REACTED WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF (1) A LOWER ALIPHATIC ALDEHYDE AND (II) A LOWER ALIPHATIC ALDEHYDE AND ALCOHOL; (C) A SOLVENT FOR SAID RESIN AND SAID CROSS-LINKABLE AGENT; (D) AN ACID CATALYST ADAPTED FOR CROSS-LINK ING SAID RESIN WITH SAID CROSS-LINKING AGENT; AND (E) AN ORGANIC LIQID ADAPTED FOR MIXING WITH THE BLANCE OF SAID COMPOSITION TO FORM GLOBULES THEREIN, SAID ORGANIC LIQUID COMPRISING AT LEAST 89% BY VOLUME PARAFFINIC HYDROCARBONS AND HAVING A BOILING POINT OF AT LEAST ABOUT 300*F.
 2. The composition of claim 1 wherein the cross-linkable resin is a cellulose acetate butyrate or cellulose acetate propionate.
 3. The composition of claim 1 wherein the organic liquid comprises mineral spirits or Stoddard solvent.
 4. The composition of claim 1 wherein said catalyst is selected from the class consisting of p-toluene sulfonic acid, alkane sulfonic acid, sulfuric acid, hydrochloric acid, and nitric acid.
 5. A coating composition adapted to form an opaque color when applied to a substrate and cured thereon, said coating composition consisting essentially of (a) 2 to 20% by weight cellulose acetate butyrate or cellulose acetate propionate having an hydroxyl content of from 4-7%; (b) 2 to 20% by weight of a condensation polymer of a compound selected from the group consisting of 1) a urea compound, 2) thiourea, 3) cyanamide, 4) guanidine, and 5) melamine reacted with a compound selected from the group consisting of 1) a lower aliphatic aldehyde, and 2) a lower aliphatic aldehyde and alcohol; (c) 6 to 60% by weight solvent for said propionate or butyrate and said condensation polymer; (d) 0 to 4% by weight plasticizer; (e) 0.025 to 2% by weight acid catalyst adapted for promoting cross-linking of said butyrate or propionate with said condensation polymer; (f) 12 to 40% by weight hydrocarbon-type organic liquid adapted for mixing with the balance of said composition to form globules therein, said organic liquid comprising at least 85% by volume paraffinic hydrocarbons and having a boiling point of at least about 300*F; and (g) 0 to 10% by weight modifying resin.
 6. The composition of claim 4 wherein said catalyst is aged prior to addition to said composition by boiling the catalyst in a higher-boiling point solvent for about 2 hours and storing the boiled catalyst for at least a week prior to use.
 7. The composition of claim 5 wherein the modifying resin is an epoxy, phenolic, blocked isocyanate, or polyvinyl butyral resin. 